Three-dimensional Porous Framework Research Articles

Functional covalent organic framework illuminate rapid and efficient capture of Cu (II) and reutilization to reduce fire hazards of epoxy resin

A key challenge for decontamination technologies is to study adsorbents possessing abundant approachable binding sites to realize rapid and effective capture of heavy metal ions in contaminated water. Herein, a three-dimensional porous covalent organic framework (COF) was synthesized, which can function as a scaffold for decorative binding sites. Considering the plentiful functional groups such as catechol groups of polydopamine (PDA), the decoration is demonstrated by coating PDA on the surface of COF via self-polymerization of dopamine under alkaline conditions. The obtained PDA-coated COF (COF@PDA) shows high affinity for copper ions (Cu (II)), while its adsorption capacity reaches 109.2 mg g−1 according to the Langmuir fitting. It takes only 10 min to achieve adsorption equilibrium and its equilibrium data follows pseudo-second-order kinetic model. Thermodynamic studies confirmed a spontaneous and exothermic removal process in essence. To achieve cyclic utilization of Cu (II), the adsorbed Cu (II) ions were heat-treated into CuO to obtain CuO-loaded COF@PDA (COF@PDA@CuO). It can serve as flame retardant for reducing fire hazards (heat, smoke and toxic gas) of epoxy resin (EP), thus confirming its dual functionalities towards environmental remediation and application as flame-retardant.

Functional covalent organic framework for exceptional Fe2+, Co2+ and Ni2+ removal: An upcycling strategy to achieve water decontamination and reutilization as smoke suppressant and flame retardant simultaneously

• The polydopamine-modified covalent organic framework (COF@PDA) was obtained. • Ultrafast and effective removal of Fe 2+ , Co 2+ and Ni 2+ for COF@PDA was identified. • The adsorbed Fe 2+ , Co 2+ and Ni 2+ was heat-treated to form its corresponding metal oxides. • The COF@PDA@Metal oxides were efficiently recycled to reduce the fire hazards of PS. A key challenge for wastewater remediation is to develop desirable adsorbents possessing abundant approachable binding sites to realize both ultra-fast capture and ultra-high absorbance for heavy metal ions. Herein, we illustrate how the three-dimensional porous covalent organic framework (COF) displays the right combination of properties, thus offering a platform for decorative chelating sites to address heavy-metal poisoning. The rational design is demonstrated by modifying polydopamine (PDA) on COF, which aims at anchoring plentiful functional groups, especially catechol groups to bind heavy metal ions. The obtained PDA-coated COF (COF@PDA) achieves rapid capture of Fe 2+ , Co 2+ and Ni 2+ , and reaches adsorption equilibrium within 10 s. According to the Langmuir fitting, the calculated capture capacities of COF@PDA for Fe 2+ , Co 2+ and Ni 2+ equal 204.9, 194.2, and 207.5 mg/g, respectively. Thermodynamic studies confirmed the spontaneous and exothermic characteristic of the adsorption process. Adhering to the concept of green chemistry and sustainable development, the good catalytic performance of transition metal ions intrigues us to further investigate its flame retardant application after recovering from sewage. The “recycling” strategy of adsorbed metal ions enables the reduction of fire hazards (heat, smoke and toxic gas) of polystyrene (PS) while retaining the mechanical properties of PS composites.

(Invited) Bottom-up Growth of Lithium in Three–Dimensional Porous Framework Electrodes

The Li metal anode has attracted much attention, because of its high specific capacity and low electrochemical potential. However, its commercial viability is hindered by the uncontrollable growth of Li dendrites as well as large volume changes over battery cycling. Li storage in three-dimensional (3D) porous framework electrodes of metals and carbon is believed to be effective for resolving those problems with 2D Li metal. However, 3D framework electrodes still suffer from uneven Li plating–stripping: during Li plating, Li preferentially nucleates and grows on top of the framework electrode (facing the separator) because the ionic resistance of electrolyte-filled pores inhibits the migration of Li+ deep into the electrode bottom (facing the current collector). The so-called “top growth” becomes severe in the presence of any protrusions or roughness on the top surface due to the concentrated Li+ flux. In contrast to the general expectations, therefore, the 3D framework electrodes tend to exhibit poor cycling stability and early cell failure. Herein, we present a combined modeling and experimental study showing the manipulation of the Li plating behavior in the 3D framework electrode via interfacial activity tuning. Based on the understanding of the multiple reaction kinetics in the porous framework electrode, we propose an interfacial activity gradient (IAG) design as an effective approach to enable the “bottom-up growth” of Li even without rigorous optimization of porous structures. The Li plating behaviors are theoretically studied on a “model” architecture via transmission line modeling and are experimentally proved. The theoretical and experimental results are in accord with each other, indicating that the IAG design enables the bottom-up growth of Li within the 3D framework electrode, while suppressing the top growth. The IAG electrode exhibits the outstanding improvement in morphological stability and electrochemical reversibility as compared with the conventional framework electrode with uniform interfacial activity.

Electrophoretic Deposited Black Phosphorus on 3D Porous Current Collectors to Regulate Li Nucleation for Dendrite-Free Lithium Metal Anodes.

Li metal is considered a highly desirable anode for next-generation high-energy-density rechargeable lithium batteries. However, irregular Li dendrite formation and infinite relative volume changes prevent the commercial adoption of Li-metal anodes. Here, electrophoretic deposition of black phosphorus (BP) on commercial Cu foam (BP@Cu foam) is reported to regulate Li nucleation for the first time. First-principles calculations reveal that the unique two-dimensional (2D) structure of BP is beneficial to Li intercalation and propagation. Compared with the random Li nucleation and growth on bare Cu foam, Li ions are preferably confined into the BP layers, which induces uniform Li nucleation at the early stage of the Li deposition and guides the following lateral Li growth on BP@Cu foam. In addition, the three-dimensional (3D) porous and conductive framework of Cu foams further mitigate the volume change and dissipate the current density. Attributing to these merits, the BP@Cu foam exhibits significantly enhanced Coulombic efficiency and cycling stability compared with bare Cu foam. In the full-cell configuration paired with a Li4Ti5O12 or LiFePO4 cathode, the BP@Cu foam also boosts the battery performances. This work provides new insights into the development of BP and other elaborate 2D materials for achieving dendrite-free Li-metal anodes.

Recycled silicon-based anodes with three-dimensional hierarchical porous carbon framework synthesized by a self-assembly CaCO3 template method for lithium ion battery

Silicon/carbon composite anodes with void space are widely touted as a promising candidate for lithium-ion batteries (LIBs), providing a good volume change tolerance to maintain the integrity of the electrodes. However, the void space is usually created by complicated and environmentally-unfriendly methods with corrosive HF. Herein, a 3D hierarchical porous carbon framework supported silicon-based composite with void space (Si@Voids@PC) is synthesized by diluted HCl-assisted etching a self-assembly CaCO3 template method coupled with pyrolysis of citric acid as the carbon source. The Si@Voids@PC electrode exhibits reversible capacity retention of 1527 mAhg−1 at 200 mAg−1 after 200 cycles with an initial discharge specific capacity of 3060.6 mAhg−1 and an initial Coulomb efficiency of 74.4%, which is superior to most of that in the reported literatures. This unique structure can not only provide more pathways for lithium ion diffusion and electron transfer but also maintain the integrity of the electrodes. Besides, the effect of lithiation behavior on the solid electrolyte interphase (SEI)-related problems is observed and discussed. This work might provide a facile and green method to synthesize silicon-based anodes with excellent electrochemical performance, and it also can be applied to the design of other materials with porous architecture.

Three-dimensional zanthoxylum Leaves-Derived nitrogen-Doped porous carbon frameworks for aqueous supercapacitor with high specific energy

A unique three-dimensional zanthoxylum leaves-derived nitrogen-doped porous carbon frameworks (ZLPC) with hollow nanostructures have been developed by one-step carbonization and mixed metal salts-assisted co-activation process. Compared with the traditional template carbonization or two-step carbonization strategy, the presented method can combine carbonization, activation and heteroatom doping to improve the synthesis efficiency. Based on the unique three-dimensional framework structure, large specific surface area, high graphitization degree and effective nitrogen doping, the ZLPC exhibits satisfactory electrochemical performance. In particular, the symmetric supercapacitor based on ZLPC electrode material possesses high specific energy of 18.68 Wh kg−1 at a specific power of 225 W kg−1 operated in the voltage of 1.8 V in Na2SO4 aqueous electrolyte and excellent cycle stability (92% after 20,000 charge cycle). These results provide a clear, simple and feasible synthesis strategy for large-scale converting sustainable biomass waste to porous carbon materials for energy storage and conversion applications.

MnCO3 on Graphene Porous Framework via Diffusion-Driven Layer-by-Layer Assembly for High-Performance Pseudocapacitor.

Diffusion-driven layer-by-layer (dd-LbL) assembly is a simple yet versatile process that can be used to construct graphene oxide (GO) into a three-dimensional (3D) porous framework with good mechanical stability. In particular, the oxygen functional groups on the GO surface are well retained, providing nucleation sites for further chemical reactions to be performed upon. Therefore, such a scaffold should serve as a promising starting material for creating a wide range of 3D graphene-based composites while maintaining a high accessible surface area. Herein, we demonstrate the use of the porous GO macrostructure derived from dd-LbL assembly for the preparation of graphene-MnCO3 hybrid structures. MnCO3 is a newly reported pseudocapacitive material for supercapacitors; however, its electrochemical performance is hampered by its low electrical conductivity and poor chemical stability. Through reaction between KMnO4 and GO during a hydrothermal process, the surface of the porous scaffold was rendered with uniform MnCO3 nanoparticles. With the reduced graphene oxide (rGO) sheets serving as the conductive backbone, the resultant MnCO3 nanoparticles exhibited a capacitance of 698 F g-1 at a charge/discharge current of 0.5 mA (320 F g-1 for the combined rGO and MnCO3 composite). Furthermore, the electrode maintained 77% of its initial capacity even after 5000 cycles of charge/discharge tests at 20 mA.

Multi-dimensional ZnO@MWCNTs assembly derived from MOF-5 heterojunction as highly efficient microwave absorber

Metal-organic framework (MOF) derivatives have been arousing great attention in microwave absorption (MA) applications because of the adaptable morphological and component variance. However, it is still a huge challenge to construct multi-dimensional assembly with special heterostructure based on MOF and conductive carbon materials for excellent MA performance. Here, we successfully synthesized the cube-like assembly of multi-walled carbon nanotubes (MWCNTs) and ZnO (ZnO@MWCNTs) with unique multi-dimensional architecture via controlling the pyrolysis time of MOF-5 wrapped by MWCNTs. The ZnO@MWCNTs-4h are composed of zero-dimensional ZnO nanoparticles, one-dimensional MWCNTs, and three-dimensional micro-scale porous carbon framework. These various dimensional components confined within the cube space lead to the strong reflection loss (RL) at different frequencies, thus resulting in exceptional MA performance. The ZnO@MWCNTs-4h can reach a RL peak of −34.4 dB at only 1.5 mm thickness. More importantly, the maximum RL can achieve −47.4 dB at 2.7 mm with a mass loading as low as 20%. The optimized MA performance can be ascribed to high-density polarized sites, tightly interwoven MWCNTs conductive network, and strong multiple scattering that all induced by the multi-dimensional structures and components. Therefore, novel ZnO@MWCNTs composites are promising as a lightweight and highly efficient microwave absorber.

Hydrogel derived FeCo/FeCoP embedded in N, P-codoped 3D porous carbon framework as a highly efficient electrocatalyst for oxygen reduction reaction

Numerous studies have been focused on renewable energy conversion devices (e.g. fuel cell and Zn-air battery) to mitigate the climate changing and serious environmental degradation. Herein, hydrogel derived FeCo/FeCoP embedded in N, P-doped three-dimensional porous carbon framework (FeCo/FeCoP@NP-CF) was prepared by the high-temperature pyrolysis and subsequent acid-etching. Polyacrylamide (PAM) would absorb water here to form hydrogel and act as the C and N sources, which is conducive to capture and in-situ reduce metal ions. The hybrid porous carbon framework had interconnection, highly open structures and molecular accessible hierarchical surfaces. The resultant FeCo/FeCoP@NP-CF displayed remarkable oxygen reduction reaction (ORR) characteristics with a more positive half-wave potential (E1/2) of 0.85 V in 0.1 M KOH electrolyte, surpassing commercial Pt/C (E1/2 = 0.84 V). This work offers some valuable guidelines for synthesis of non-noble metal catalysts in energy technologies.

Bottom-Up Lithium Growth Triggered by Interfacial Activity Gradient on Porous Framework for Lithium-Metal Anode

Three-dimensional (3D) porous frameworks have attracted considerable interest as lithium-metal electrodes for next-generation rechargeable batteries. The high surface areas and large pore volumes o...

A sandwich electrochemiluminescent assay for determination of concanavalin A with triple signal amplification based on MoS2NF@MWCNTs modified electrode and Zn-MOF encapsulated luminol.

An ultrasensitive sandwich electrochemiluminescence (ECL) biosensor was designed for determination of concanavalin A (ConA) through the specific carbohydrate-ConA interactions. Three-dimensional porous metal-organic framework (Zn-MOF) was synthesized, which loaded a large amount of luminescent reagents as luminol by encapsulating into its pores to form Zn-MOF@luminol complex. Interestingly, Zn-MOF also acted as the coreactant accelerator in the luminol-H2O2 ECL system. This Zn-MOF@luminol complex was used as the signal probe to achieve a super strong and stable ECL signal. In addition, three-dimensional hierarchical molybdenum disulfide nanoflower and multiwalled carbon nanotubes complex (MoS2NF@MWCNTs) with peroxidase-mimicking enzyme property were used as a substrate to modify the glassy carbon electrode to further enhance the ECL signal of luminol by promoting decomposition of H2O2 into reactive oxygen species (ROSs). In addition to the horseradish peroxidase (HRP) catalysis effect on the luminol ECL signal, a triple amplified ConA sandwich ECL sensor with high sensitivity sensor was constructed. The linear range for ConA detection was from 0.5pg/mL to 100ng/mL with a detection limit of 0.3pg/mL (S/N = 3). The recovery test for ConA in human serum samples was performed with satisfactory results. Graphical abstract.

Enhanced peroxymonosulfate activation process based on homogenously dispersed iron and nitrogen active sites on a three-dimensional porous carbon framework

Developing transition metal/nitrogen/carbon catalysts with maximizing the dispersion degree of the active sites presented an enticing prospect for environmental remediation. In this study, we have designed the novel three-dimensional porous carbon aerogel (CA) supported iron and nitrogen co-doped carbon (FeNC-CA) catalysts via facile pyrolysis of iron phthalocyanine (FePc) confined within CA precursor by the double fixed-protection strategy. The synergistic enhancement effect between CA and well-dispersed FeNC in FeNC-CA-500 (pyrolysis at 500 °C) was conducive to the rapid removal of 4-chlorophenol (4-CP) via peroxymonosulfate activation, which achieved almost 100% removal efficiency and 66.8% mineralization rate in 18 min with ultralow catalyst dosage and iron ions leaching of 0.019 ppm, and the reaction rate constant was about 11.3, 9.3 and 6.6 times higher than that of the homologous FeNC-500, CA-500 and Fe-CA-500 catalysts, respectively. Based on the electrons spin resonance (ESR) and radical quenching experiments, the FeNC-CA-500/PMS system with selective removal ability of several aromatic compounds containing different substituents and strong flexibility in actual wastewater involving competing inorganic ions and natural organic matter confirmed that the nonradical pathway was dominant in 4-CP removal while the generated reactive oxygen species (ROS) played a relatively small roles. Further investigations by X-ray photoelectrons spectroscopy (XPS) and control experiments verified that the evenly dispersed iron active sites were essential in accelerating the catalytic reaction, and the carbon matrix and surface nitrogen sites were mainly responsible for the removal rate of 4-CP via nonradical pathway. These findings provided new insights for synthesis of a more promising iron-based catalyst for practical wastewater treatment.

One-step production of carbon nanocages for supercapacitors and sodium-ion batteries

Abstract Utilizing biomass to produce high-performance energy-storage materials has been the focus of increasing attention, thanks to the low cost, renewability, environmental friendliness, and inherent nature of certain biomass. However, the applications of biomass-derived carbons are commonly confined by their low electrical conductivity and ion diffusion kinetics. In this work, we report one-step strategy of synchronous activation and graphitization, using a new activating agent, i.e. KMnO4, to produce three-dimensional (3D) hierarchical porous framework of carbon nanocages (FCNC) from biomass for both supercapacitors and sodium-ion batteries (SIBs) applications. As a result, high specific capacitances (490.7 F·g−1 at a charge density of 1.0 A·g−1 in a three-electrode system using 6 mol·L−1 KOH aqueous as electrolyte) and high energy density (92.0 Wh kg−1 at power density of 1800 W·kg−1 using EMIMBF4 electrolyte) have been demonstrated when applying FCNC in supercapacitors, and high reversible capacity of 318.2 mAh·g−1 at 50 mA·g−1 has been achieved in SIBs. Although the rate performance is one of the primary concerns of SIBs, a high retention rate of 92% is realized in the present case after 1000 cycles at 10 A·g−1. Excitingly, even at 10 A·g−1, the reversible capacity delivered by FCNC maintains to be as high as 81.6 mAh·g−1.

5-Fluorouracil Trapping in a Porous Ba(II)-organic Framework: Drug Delivery and Anti-thyroid Cancer Activity Evaluation

Solvothermal treatment of Ba(NO3)2 with the rigid tricarboxylic acid linker 4,4′,4″-s-triazine-2,4,6-triyltribenzoic acid (H3TATB) in a mixture of H2O and N,N-dimethylformamide (DMF) produces a new three-dimensional porous metal-organic framework having the chemical formula of [Ba(HTATB)-(H2O)2](DMF)4 (I). The complex I has been characterized by powder X-ray diffraction, elemental analysis and single crystal X-ray diffraction (CIF file CCDC no. 1898532). In light of its large inner spaces as well as widely distributed open metal sites, the guest-free I (Ia) has been used as a crystalline vessel for trapping the anticancer drug 5-fluorouracil (5-FU), which has been investigated both experimentally and computationally. Furthermore, MTT assay was employed to evaluate the in vitro cytotoxicity of the carrier 5-FU loaded Ia against the human thyroid cancer cell lines.

A new molybdovanadate [V3Mo8O36H2]7−: Synthesis, crystal structure and electrochemical sensing properties

A new molybdovanadate [NH4]6[Na(H2O)][V3Mo8O36H2]·16H2O (1) was isolated by a one-pot self-assembly synthesis strategy, which presented a three-dimensional (3D) porous framework based on the novel molybdovanadate [V3Mo8O36H2]7− building blocks bridged by Na+ cations. The modified electrode is prepared by utilizing compound 1 as electrode active material, exhibiting fast response, wide detection range, and high sensitivity for the detection of ascorbic acid.

Polymorphism and Molten Nitrate Salt-Assisted Single Crystal to Single Crystal Ion Exchange in the Cesium Ferrogermanate Zeotype: CsFeGeO4.

Two polymorphs of a new cesium ferrogermanate zeotype, CsFeGeO4, were synthesized using the molten CsCl-CsF flux growth approach at 900 °C. The orthorhombic polymorph, referred to as (1), crystallizes in the centrosymmetric nonpolar Pbcm space group. The compound exhibits a three-dimensional porous framework structure composed of disordered (Fe/Ge)O4 corner-sharing tetrahedra that generate large eight-sided channels running down the b-axis. These channels are occupied by Cs ions that provide charge balance to the anionic framework. Minor modifications in the reaction conditions lead to the synthesis of a monoclinic polymorph of CsFeGeO4, referred to as (2), crystallizing in the noncentrosymmetric polar space group P21 and exhibiting an identical framework structure to (1), albeit featuring ordered FeO4 and GeO4 tetrahedra. Solid state synthesis of CsFeGeO4 produces a polycrystalline mixture of (1) and (2), referred to as (6). Polarization-electric field (P-E) measurements of (6) indicate that the material is not ferroelectric. Powder second harmonic generation (SHG) measurements of (2) and (6) revealed them to be SHG active with intensities of 1.5 and 0.2 times that of α-SiO2, respectively. The temperature dependent magnetic susceptibility of (2) exhibits a downturn at T = 2.6 K, indicative of antiferromagnetic ordering. First-principles calculations in the form of density functional theory showed that (1) and (2) differ in stability by only 1.3 meV/atom, with (2) being the thermodynamically stabilized phase. Additional calculations for (1), using molten nitrate as reference, predicted the formation of energetically favorable phases, KFeGeO4 (3) and RbFeGeO4 (4). They were subsequently prepared via a molten nitrate salt bath treatment of (1) to replace Cs with K and Rb, affording (3) and (4) as single-crystal to single-crystal ion exchange products. Structure determination and property measurements for a pyroxene phase, CsFeGe2O6, referred to as (5), are also reported. This compound crystallized as a side product in the flux synthesis of CsFeGeO4.

A free-standing and flexible phosphorus/nitrogen dual-doped three-dimensional reticular porous carbon frameworks encapsulated cobalt phosphide with superior performance for nitrite detection in drinking water and sausage samples

An assembly and self-template strategy is presented for the synthesis of cobalt phosphide nanoparticles (CoPx, x = 1, 2) embedded into 3D phosphorus/nitrogen co-doped reticular porous carbon frameworks (denoted as CoPx@P,N–RPCs) utilizing polyacrylonitrile (PAN) as the in situ nitrogen doping carbon source and hypophosphite as phosphorus source via hydrothermal method and subsequent phosphorization. The obtained CoPx@P,N–RPCs nanocomposite possesses the inherent features of both unique 3D porous structure and hierarchical connectivity, providing highly efficient pathways for electron, ion, and mass transport. The unique P,N co-doped carbon network confines nanostructural CoPx into the microstructural carbon network, which prevents them from aggregating, improves the conductivity of CoPx, meanwhile alleviates large volume expansion/contraction effect, thus results in high electrochemical performance and cycling durability. Benefiting from its unique structural advantages, the CoPx@P,N–RPCs nanocomposite exhibits excellent electrochemical performance for nitrite (NO2–) detection with a wide linear range of 10 nM to 1.184 mM, a low detection limit of 5 nM, and a very high stability, which is better than most nitrite sensors reported previously. Importantly, the nitrite level can be determined by the resulting sensor in food and drinking water with excellent recoveries, implying its feasibility for realistic application.

Synergistically enhanced sodium/potassium ion storage performance of SnSb alloy particles confined in three-dimensional carbon framework

In this work, an efficient composite of SnSb alloy particles confined in three-dimensional porous carbon framework (SnSb@C) is rationally designed and fabricated by means of NaCl template-assisted in situ freeze-drying treatment and subsequent thermal reduction method. Benefit from rational material design and the excellent structural features of the active materials, the SnSb@C can deliver a high initial reversible capacity of 457 mA h g−1 at 100 mA g−1, and excellent cycling stability with capacity retention of 84% after 200 cycles at 0.1 A g−1, when evaluated as an anode material for SIBs. Meanwhile, the SnSb@C electrode can also deliver a high reversible discharge capacity of 293 mA h g−1 at 100 mA g−1 after 100 cycles in PIBs with good rate capability and impressive cycling performance. These results demonstrated that the SnSb@C composite is a promising anode material for future high-performance SIBs and PIBs.

Multi‐metal doped high capacity and stable Prussian blue analogue for sodium ion batteries

Prussian blue analogues (PBA) are attractive positive electrode for sodium ion batteries due to their large interstitial sites and three-dimensional porous framework. However, they often suffer from irreversible phase transition upon charging and discharging, leading to fast capacity decay. In consideration that redox couples of Co2+/Co3+, Ni2+/Ni3+ and Fe2+/Fe3+ guarantee high capacity (~150 mA h g−1), and Cu serves as a pillar to hold the PBA framework, here we synthesized a series of Cu, Co and Ni co-doped PBA, displaying high capacity and stable cycling performance with >98% capacity retention after 50 cycles.

1,3,5-Triethynylbenzene and melamine as monomers to synthesize three-dimensional network porous aromatic frameworks based silica/florisil for determination of carbendazim and thiabendazole in spinach.

In this study, the new and efficient three-dimensional network porous aromatic frameworks materials called Silica-PAFs-a, Florisil-PAFs-a, Silica-PAFs-b, and Florisil-PAFs-b were first synthesized. The properties of materials were analyzed by five characterization methods. The materials were used as adsorbents in pipette-tip solid-phase extraction for the effective determination of carbendazim and thiabendazole in spinach sample. Meanwhile, the obtained materials were tested by static adsorption and dynamic adsorption. The result showed that the specific surface area of materials greatly increased after introducing three-dimensional network porous aromatic frameworks. Microstructural modification exposed a large number of amino reactive groups that made them have a better adsorption amount for the two targets. The calibration graphs of carbendazim and thiabendazole in methanol were linear over 0.10-300.0µg/mL, and the limits of detection and quantification were 0.00546 and 0.0182µg/mL, and 0.00741 and 0.0247µg/mL respectively. A reliable analytical method was developed for recognition targets in spinach sample by Silica-PAFs-b with satisfactory extraction recoveries (96.25 and 100.51%). The proposed method using the material was applied for trace analysis of the carbendazim and thiabendazole residue.